Formed into monoalkylamino-oxyaryl compounds and process of making



UNITED s'rATns ra ere EMIL REBER AND J OSEF SIEGWART, OF B ASEL, SWITZERLAND, ASSIGNORS TO SOCIETY OF CHEMICAL INDUSTRY IN BASLE, OF BASEL, SWITZERLAND.

N-MONOARYLSULFO-MONOALKYLAMINO-OXYARYL COMPOUNDS ABLE TO BE TRANS- FORMED INTO MONOALKYLAMINO-OXYARYL COMPOUNDS AND PROCESS OF MAKING SAME.

No Drawing.

To all whom it may concern Be it knownthat we, EuiL Human and JOSEF SIICGWART, both citizens of the Swiss Republic, and residents of Basel. Switzerland, have invented new and useful N-monoarylsulfomonoalkylan'iino oxyaryl c o m pounds able to'be transformed into monoalkylamino-oxyaryl compounds and process of making same. of which the. following is a full. clear. and exact specification.

We have found that the esters of the N- niouio-arylsulfoaniino-oxyaryl con'ipounds of the general. formula (wherein R stands for an aryl radical, as

In benzene. Solubility in alcohol. In glacial acetic acid. Constitution. Fusion poin't.

Cold. Hot. Cold. Hot. Cold. Hot.

Melliylderivative 7 162 C. dilllcultly solueasily soluble. very diflicultly (limeultly solu' somewhat dimeasily soluble. soluble hle. cultly soluble. ble.

' Ethyl-derivative l i 117C. somewhateasily easily soluble. dillicultly solusomewhateasily somewhateasily easily solusoluble. ble. soluble. soluble. ble.

Benzyl derivative..... 142 C diflicultly solueasily soluble. very dimcultly dimcultly soludilfieultly solueasily solublc. soluble. ble. ble. ble.,

.-\ll vl-derivative 113 C. diflleultly solueasily soluble. (liflicultlysolusomewhateasily somewhat dilfieasily soluble. ble; soluble. cultly soluble. blo.

The process is illustrated by the following are dissolved at. (50 C. in 120 parts of Wafor instance phenyl or naphthyl. R for an arylsulfo radical and R- for an acidvl radi- 'cal, as for instance an arylsulfo radical) can'he converted smoothly into new estersof the N moimarylsulfomonoalkylamino-oxyar vl-eompounds. by treating them \vith'the usual all vlatin1 agents. as for instance. diallevlsulfates, arylsulfoalkylesters, alkyl halids, preferably in presence of an alkali.

Specification of Letters Patent.

Patented Sept. 23, 19119.

Application filed August 17, 1918. Serial No. 250,323.

These newesters of the N-n'ionoarylsulfomonoalkylamino-oXyarylcompounds can be employed as parent materials for the manufacture of monoalkylamino oxyaryl com pounds of the general formula (wherein R stands for an ary] radical and R for an alkyl radical, as for instance a methyl radical). For this purpose the said new esters are treated with saponifying agents.

The new esters of the N-monoarylsulfonionoalkylamino-oxyaryl-conipounds are colorless substances insoluble in water, (soluble in the organic solvents and crystallizing well tllQlGfIOll'l and-melting at determined temperatures.

The solubilities in organic solvents and the fusion points of several paratoluenosulfoesters of N-paratoluenosulfo-monoalkylpara-amidophenols are indicated in the fol lowing tabular exhibit:

examples Example 1. v +1.7 parts of raw N-toluenosulfo-paraaminophenoltoluenosulfoester of the formula O-SOZ.C;H4.CH;

ter and 16 parts of concentrated soda lye 0f per cent. From the solution filtered the pure sodium salt of the N-toluenosulfopara amino phenol tohmlsulfoester separates, on cooling,' nearly quantitatively in form of lamellar White crystals.

W-hen 22 parts of this sodium salt are heated in a closed vessel with 50 parts of methylalcohol and 2:}: to 3 parts of methylchlorid, at 100 to 120 C. for several hours, the N-toluen0sulfomonomethyl-para-aminophenoltoluenosulfoester is obtained, which separates nearly quantitatively in form of white small needles melting at 162 C.

. The alkylation with other alkylating agents, as ethyl halid, allylbromid, ethylene bromid, benzylchlorid, 'etc., occurs in an analogous manner, in certain cases also in an open vessel provided w1th a reflux cooler,

whereby other agents, as ethylalcohol, water,

etc., maybe employed as diluting agentsor solvents v I v The corresponding derivatives of orthoor -metaan 1inophenol or of the aminona hthols and their substitution products, which are substituted in the aminogroup by an arylsulforadical, in the hydroxylgroup by an acidyl radical, can also be alkylated easily.

The alkylation occurs also very smoothly when arylsulfoalkylesters or dimethylsulfate are employed as alkylating agents.

Example 2.

When 41.7 parts of N-toluenosulfo-paraaminophenoltoluenosulfoester are dissolved in the tenfold quantity of water and 15 parts of concentrated soda lye at 40 to C. and 13 parts dimethylsulfate are added to the solution thus obtained, while stirring, the pure methylderivative separates after a short time quantitatively.

In an analogous manner the alkylationcan be effected with arylsulfoalkylesters as for instance toluenosulfomethylester, etc. he transformation of the new-N-toluenosulfomonomethyl-para-aminophenoltoluenoing in treating with alkylating agents the oxyaryl-compounds.

compounds of the general formula R NHR1 02a (wherein R stands for an aryl radical, R

for an arylsulforadical and R for an acidyl radical).

esters of N-monoarylsulfoamino-0Xyaryl-' 2. The herein described process for the manufacture of N-toluenosulfomonomethylpara aminophenoltoluenosulfoester consisting in treating with: a methylating agent the sodium salt of the N-toluenosul o aminophenoltoluenosulfoester.

3. As new products the herein described esters of N monoarylsulfo-monoalkylaminooXyaryl-compounds of the general formula v I R! (wherein-R stands for an aryl radical, R

for an arylsulfo radical and R for an acidyl radical and R for an alkyl radical) which constitute colorless substances of definite fusion points, insoluble in water, soluble in organic solvents and crystallizing well therefrom and able to be transformed by their saponification into monoalkylamino- 4. As a new article of manufacture the herein described N-toluenosulfo-monomethyl-para-aminophenol -toluenosulfoester,,

constituting a colorless substance insoluble in water, difli'cllltly soluble in cold benzene, easily soluble in hot benzene, difiicultly soluble in alcohol, crystallizing in the form of small needles melting at 162 C. and able to be transformed by saponification into N --mon0methyl-para-aminophenol.

In witness whereof we have hereunto signed our names this 26th day of July,

1918, in the presence of two subscribing witnesses.

EMIL REBER. J OSEF I SIEGWART. Witnesses:

H. H. DicK,

- ORMANi) RITTER. 

